Process for breaking petroleum emulsions



- curring waters or brines .uct se s o pu o e emulsions of the water-in oil type, I particularly of the free base or Patented May 25, 1954 PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin -De Groote, University City, ;Mo., assignor to Petrolite Corporation, -Wilmington, De l,, a corporation of Delaware No Drawing. Application June27, 1952, Serial No. 296,084

16 Claims. (01. 352-9344.)

This invention relates to processes or procedures particularly adapted for preventing, break- ;ing or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions.

, I he present invention is a continuation-inpart of my copending application, Serial No.

seems, filed May 19, 1952.

; My invention provides an economical and rapid ;p1'oces s f0r resolving petroleum emulsions of the water in-oil type, that are commonly referred to :as cut oil, roily oil, emulsified oil, etc., and

which comprise fine droplets of naturally ocdispersed in a more or less permanent state throughout the oil which constitutes the continuous sion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removin impurities, particularly inorganic salts,

from pipeline oil.

The demulsifying agents employed in the present demulsifying process are the products obtained by the process of condensing (a) an oXyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, Water-insoluble,

lowstage phenol-aldehyde resin of the type described hereinafter as component (a) in Part 1; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature suhiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting fromthe process be heat-stable and o igyalkylation-snsceptible.

As far as the use of the herein described prodof resolution of petroleum prefer to use those which as such or in the form hydrate, i. e., combination with water orparticularly in the form of a low gnolal organic acid such as the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a Water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensationiproductsas such or-in theform of the free phase of the emulbase or in the formof the acetate, may notnecessarily be xylene-soluble although they are in many instances. ;If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some "suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether,=or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with :the equal weight of xyl ene, followed by addition of Water. Such test is obviously the same for the reason-that there will be two phases on vigorous shaking and surface activity makesitspresence manifest. It is understood'the reference'inthe hereto appended claims asto-thense'of .xylene in the emulsification test includes such obvious variant.

Reference is again made .to U. :8. Patent 2.499368, dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent-the following test appears:

-The-sameristrue inregard to the oxyalkylated resins herein specified, particularly in the lower stage .of oxyalkylation, the so-called sub-surfaceactive stage. Ehesurface-active properties are readily demonstrated by producing a xylenewater emulsion. Asuitable procedure is as follows: "If-he oxyalkylated resin is dissolved in an equal weight of gxylene. Such 50-50 solution is :then mixed with 1-3 volumes of Water and shaken to produce an (emulsion. reduce even a. tacky resinous product to a solution which is readily dispersible. The emulsions so produced are -usually xylene-in-water emulsions (oil-in-water type) particularly when the amount of distilled water used is at :least slightly in excess of the I, solution and also if shaken vigorously. -;At times, particularly in the lowest stage of oxyalkylation, one may obtain a waterin-xyleneemulsion water-in-oil type) which is apt to reverse on more vigorous shaking and further vdilution with water.

If in doubt as to this property, comparison with ,a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to l 1.1 formaldehyde) usingan acid catalyst and then followed by oxyalkylation using 2 moles of ethyl- .ene oxide for each phenolic hydroxyl, is helpas described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are use ful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-freeproduct on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approxi' mate point Where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of th material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are Such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immateria1 whether a xylene solution produces a sol or whether it merely produces an emulsion.

For convenience, what is said hereinafter will be divided into five parts:

Part 1 is the introductory part as far as the demulsifying agents themselves are concerned, 1. e., the amine-modified resins;

Part 2 is concerned with the general structure of the amine-modified resin and also the resin itself, which is used as a raw material;

Part 3 is concerned with appropriate basic hydroxylated secondary monoamines which may be employed in the preparation of the herein described amine-modified resin;

Part 4 is concerned with the reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds; and

Part 5 is concerned with the use of the oilmodified resins obtained as described in Part 4 for the resolution of emulsions of the water-inoil type. I

PART 1 As previously stated, this invention is concerned with the use as demulsifiers for resolution or breaking of petroleum emulsions of the water-in-oil type of certain amine-modified resins. Such amine-modified resins have been described in the aforementioned co-pending application, Serial No. 288,743, filed May 19, 1952.

The demulsifying agents are heat-stable oxyalkylation susceptible resinous condensation products of (a) a defined phenol-aldehyde resin, (2)) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde. The condensation reaction is conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and the resultants of reaction. An other aspect of the invention, of course, is the procedure employed for making such condensation products.

The phenol-aldehyde resin designated as component (a) is an oxyalkylation-susceptible-fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight correspondin to at least 3 and not over 6 phenolic nuclei per resin molecule. The phenol-aldehyde resin is difunctional only in regard to methylol-forming activity, and the resin is derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward the phenol. Also, the resin is formed in the substantial absence of trifunctional phenols. The phenol constituent of the resin is of the formula in which R is an aliphatic hydrocarbon radical having at least '4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2, 4, 6 position.

This invention in a more limited aspect relates to the use as demulsifiers of certain amine-modified thermoplastic phenol-aldehyde resins. For purpose of simplicity the invention, as far as demulsification is concerned, may be typified by reference to the resinous materials themselves. These resins may be exemplified by an idealized formula which may, in part, be an over-simplification in an eifort to present certain resin structure. Such formula would be the following:

R n R in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

in which R represents any appropriate hydrocarbon: radical such as an alkyl, alicyclic, arylalltyl-radical; etc, with the proviso: that at: least one of the radicals designated by R has at least one hydroxyl radical. The hydrocarbon radical may have the carbon atom chain or equivalent interrupted by oxygen atoms. The only limitation is that the radical should not havea negative radical which considerably reduces the basicity of theamine, such as an aryl radical or an aoyl radical. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having. 3 to 6 phenolic nuclei as specified, alters the: resultant product in a number of ways. Inth first place, a basic nitrogen atom, or course,.adds a hydrophile effect; in the" second place, depending on the size of the radical R',.there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect morethan counterbalances the hydrophile effectof the nitrogen atom. The presence of one or more hydroxyl radicalsintroduces a significant hydrophile efiect. Finally, in such cases where R contains one or more oxygen atoms'in the form of an ether linkage anothereffeet is introduced, particularly another hydro.- phile efiect.

Combinations, resinous or otherwise, have been prepared from-phenols, aldehydes, and reactive amines, particularly: amines having secondary amino groups. Generally rials have fallen into thre'e classes; the first represents non-resinous combinations derived from phenols as such; the second class represents resins which are usually insoluble and used for thepurpose for which ordinary resins, particularly thermo-setting resins are adapted; The thirdi classrepresents resins which are' soluble as initially prepared but are not heat-stable, ii e., they are heat-convertible, which means they are not particularly suited as raw materials forsubsequent chemical reaction which requires temperatures above the boiling point of water or thereabouts.

The thirdclass of materi'alwhich of'the' three classes mentioned approaches the closest to. the herein-described derivatives or resinous amino derivatives is described in U. S; Patent. No. 2,031,557, dated February 18, 1936, to Bruson.

The resins employed as raw materials in the instant procedure are characterized by the presence: of an aliphatic-radicalin the'ortho or para position, i. e., the phenols themselves are' difunctional phenols. This is a difierentation from the'resins' described in the aforementioned Bruson. patent, No.- 2,031,557, insofar that said patentdiscloses suitable resins obtained from meta-substituted phenols, hydroxybenzene, resorcinol, p,p' (dihydroxydiphenyl) -dimethylmeth ane, and the like, all of which have at least three points of reaction per phenolic nuclei and as; a result can yield resins which. may be at least incipiently cross-linked. even though they are apparently still, soluble. in oxygenated or.- ganic solvents or else are heat-reactive. insofar that they may approach insolubility or become insoluble due to the. eifect of heat, or added formaldehyde, or both.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the stand point ofmethylol-forming. reactions. As is well known, although one may: start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei speaking, such mate- 9 have been convertedifroim a difunctionaLradical to a: trifunct'ional; radical; on im terms. of: the resin, the 1 molecule as: a; whole? has. a; methyloliforming: reactivity: greater: than 2; Such, shift cantake place afterth'e resin has been formed or during; resin. formation. Briefly, an:exampl.e iscsimply where: an alkyli radical, such; as methyl, ethyl, propyl; butyl, orrthelike; shifts from an ortho positionto; a. meta-s position, or from; a para positionlto a=meta position; For instance, in the; case: of: phenolealdehyde. varnish resins, one: canxprepareiatleastz some. inwhich: thenresins, instead 011 having; only: two points. of; reaction can have three, and possibly" more points; of reactiom. with formaldehyde; or any other. reactant: whichtends 170.. form amethylol or sub:- stitutejd' methylol group.

Apparently there is no; similar limitation: in regard to the: resins. employed in the; aforememtioned: BrusonPatenti 2,031,557, for the reason that. one may prepare.suitablearesins;from .phen'ols of. the kind already specified which invariably and inevitably" would yield a resin having a functionality greater than two inthe ultimate resin? molecule.

The resins: herein: employed are; soluble in a non-oxygenated hydrocarbon solvent, such as benzene or' xylene. As pointed out in the aforementioned Bruson' Patent 2,031,557, one of. the objectives is to convert the phenol-aldehyde resins employed as raw materials insuch: a Way as to'render'them hydrocarbon soluble; i; e;, soluble in benzene. The original resins oi U. S. Patent. 2,031,557 are selected on the basis of solubility inan oXygenatediine-rt organic solvent, such as alcohol or dioxane. It is immaterial whether the. resins: hereemployed. are soluble in dioxane or alcohol, but they must be soluble in benzene.

The-resins herein employed as raw materials must be' comparatively low molalv products having on. the average 3m 6 nuclei per resin molecule. Theresins employed in the. aforementioned U, S; Patent. No.- 2,031,557, apparently need not meet:any such limitations.

The condensation products here obtained whetherin the form of' the free base or the. salt, do not go over to the'insoluble stage-onheating. This apparently is not true of the materials described in aforementioned Bruson Patent 2,031,557, and apparently one of the objectives with which theinvention' is; concerned, is to-obtain. a: heateconvertible condensation product. The condensation product obtained according to thezpresent invention is heat stable and, infact, onexof. its'outstanding qualities is that it can be subjected to oXyalk-ylation, particularly oxyethylation" or oxypropylation, under conventional conditions,..i. e., presence of an: alkaline catalyst, for example, but in any event at a temperature above C. without becoming aninsoluble mass:

Althoughthese condensation products have been prepared primarily withthe thought in mind that they are precursors for. subsequent reaction, yet as such.- and without further reaction, they have definitely valuable: properties and? uses. as hereinafter: pointed out;

What: has. been: said.- previously in regard: to heat. stability; particularly when employed.- as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products: themselves insofar that in the condensation process employed. in preparing the compounds: described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to 140 to 150 C. If one were using resins of the kind described in U. S. Patent No. 2,031,557 it appears desirable and perhaps absolutely necessary that the temperature be kept relatively low, for instance, between C. and 100 C., and more specifically at a temperature of 80 to 90 C. There is no such limitation in the condensation procedure herein described for reasons which are obvious in light of what has been said previously.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. As pointed out in the instant invention the resin selected is xylene or benzene soluble, which differentiates the resins from those employed in the aforementioned Bruson Patent No. 2,031,557. Since formaldehyde generally is employed economically in an aqueous phase to solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two imiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and. produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or ture must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in. the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would. react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein not, ultimately the tempera- As pointed in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula in the above formula n represents a small whole number varying from 1 to 6, '7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular Weight polymers Where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to.4; R represents an aliphatic hydrocarbon substituent. generally an alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance para-phenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethylglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. see Example 9a of U. S. Patent No. 2,499,365, dated March '7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March '7, 1950. to De Groote and Keiser. In said patent there are described phenol-aldehyde resins of the type noted as component (a) in Part 1 above.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The basic hydroxylated amine may be designated thus:

1-R' .HN/

In conducting reactions of this kind one does not necessarily obtain .a fhundred :per .cent yield for obvious reasons. Certain side reactions may take place. Eor instance, 2 moles of amine may 10 combine with onemole of :the aldehyde, or only one mole of the amine may combine with the resin molecule, or :even to a very slight extent, if at all, .2 resin units may combine without any As has been pointed out.previously, as far as 3 the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde .or butyra-ldehyde. The resin unit may be exemplified thus:

R R n R in which R' is the divalent radical obtained from 1 Example Number 10 the particular aldehyde-employed to f t which are obvious the condensation product obtained appears to be described "bestin terms of the method-of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously'mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor 1 basic properties :in the i ordinary --sense orwithout any catalystatsall. .It is preferable that the resinsemployed bessubstantially neutral. In other words, if preparedby usinga strong acid as .a catalyst, suchistrong acid should be neutralized. Similarly, if .a strong .base is used as a catalyst it is preferable athatthe base be neutralized altho-ugh'l have -"found that-sometimes the reaction described proceeded more rapidly in the presence -.of asmall amount :of a free base. The-amount may be as small as ;;a

OH OH OH ZDOthofa percent and as much as afew lllths g %I ofa percent. Sometimes moderate increase in H H caustic soda and =caustic potash may be used.

' 2 However, the most desirable procedure in pr-actically every case'is to have the resin neutral. R n In preparing resins one-does not get a single OH OH OH OH 1 OH OH H n H .H. o c 0. 0* H 'H' \H H R R n R R n R polymer-pi. e., one having 'just 3units, or just "4 units, or just ;5 units, or "just 6 units, etc. It is usually a mixture; forinstance, one approximating .4 phenolic nuclei will .have,some trimerand petamer present. .may be such that .i

no reason for using other 'than those whichare lowest in price and most readily available .com-

mercially. For purposes of-;convenience suitable resins are characterized in the following table:

TABLEI ,Mol. Wt. R R derived from n of Resin Molecule N phenyl .1 3.5 992.5 tertiary butyl. .3. 5 882. 5 secondary butyl. 3. 5 882.5 cyclohexyl 3. 5 l; 025. 5 tertiary amyl. 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl. propyl para 3. 5 805. 5 tertiary hexyl. do 3. 5 1, 036. 5 octyl 3. 5 1,190. 5 nonyL. 3. 5 l, 267. 5 decyl. 3. 5 1, 344. 5 dodecyl 3. 5 1, 498. 5 tertiary butyl... 3. 5 945. 5 tertiary amyL-.- 3. .5 1,022. 5 nonyl do ;do 3. 5 1,330.5 tertiary butyl... dobutyraldehyde ,3. 5 1,071.5 tertiary amyl -do .do 3. 5 1,148. 5 nonyl do 'do 3. 5 1, 4'56. 5 tertiary butyl.-. do propion- 3J5 1,;008.5

aldehyde tertiary amyl d v 3.5 1,085. 5 nonyl d. i .3. 5 1,393. 5 tertiary buty .4. 2 996. 6 tertiary 'amyl 1 '4. 2 1, 083. 4 nonyl I :4. 2: 3,4130. 6 tertiary butyl 4. 8 1, 094. 4 tertiary amyl do 4.8 1, 189. 6 nonyl do 4. 8 1, 570. 4

suitable primary amine, such or an alicyclic amine, and

11 PART 3 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary monoamine whose composition is indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designated by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any as an alkylamine,

an arylalkylamine, treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent, or, for that matter, with an alkylating agent such as benzylchloride, esters of chloroacetic acid, alxyl bromides, dimethylsulfate, esters of sulfonic acid, etc., so as to convert the primary amine into a secondary amine. Among others, such amines include 2-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino- 2-ethyl-1,3-propanediol, and tri(hydroxymethyl)-aminomethane. Another example of such amines is illustrated by 4-amino-4-methyl-2- pentanol.

Similarly, one can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. The preparation of such amines or suitable reactants for preparing them has been described in the literature and particularly in two United States patents, to wit, U. S. Patents Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August 8, 1944, to

Spence. The latter patent describes typical haloalkyl ethers such as CHiO cznloi 021150 C2H4O 021340 021140 CZH4C1 1934, to Stallmann.

' (041100 CHzCH(CHa) 0 (CH3) CHCH2) or comparable compounds having two hydroxylated groups of different lengths as in (H0 CH2CH2O CH2CH2O CH2CH2) NH no 0211/ Other suitable amines may be illustrated by (B-GHROH HO.CH2.(3.CH2OH CH3 CHaLCHzOH 11m CHaKJHzOH any suitable alcohol or the like by reaction with V a reagent which contains an a secondary amine group. Such reactants are described, for example, in U. S. Patents Nos. 1,977,251 and 1,977,253, both dated October 16,

Among the reactants described in said latter patent are the following:

epoxide group and .since that the procedure purpose of .cluded.

instance at 150 oxygenated solvent '13 PART 4 The productsobtained by the herein described processes represent cogeneric mixtures which. are the result of acondensation reaction or reactions. Since the resin molecule cannotbe defined satisfactorily by formula, although it may be so illustrated in idealized simplification, it is diflicult to actually depict the final-product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is companable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as difierentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. a heat-reactive resin. Since the condensation products obtained are not heat-convertible and manufacture is not restricted to a single phase system, and since temperatures up to 150 .C. or thereabouts may be employed, it is obvious becomes comparatively simple. Indeed, perhaps no description is necessary :over and above what has been said previously,

in'light of subsequent examples. However, for

clarity the following details are in- A convenient piece of equipment for preparaaforementioned U. S. Patent or'low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus,

I have found it convenient to use a solvent and particularly one which can be removedreadily at a comparatively moderate temperature, for C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system.

However, if desirable, one can use an oxygenated .solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can usea comparatively non-volatile solvent such as dioxane or the diethylether ethyleneglycol. One can also use a'mixture of benzene or xylene and such oxygenated solvents. Note that the use of such is not required in the sense that it is not necessary to use aninitial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent "for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or-it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difiicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more econom- "ical. In any event, water is present as water of reaction. If the solvent is completely removed 2,031,557 in order to obtain similar solvents. .Indeed, resins which are not soluble except in at the end of the process, no problem is :involved if the material is used for any subsequent reaction. However, if the reaction mass .is going to'be subjected to some further reaction where the solvent :may be objectionable, as .in :the case of ethyl or lhexyl alcohol, and if there is :torbe subsequent oxyalkylation, then, obviously, the alcohol should snot be used .or else it should :be removed. The fact :that .an oxygenated solvent needrnot be employed, of cours.e,is an advantage for reasons stated.

Another factor, as far as the selection of .solvent goes, is whether or not the cogenericmiXturepbtained at the endofthe reaction istozbe-used as such or in the salt form. .The cogeneric mixtures obtained :are apt to be solids or thick viscous liquids in which there is some change from :the initial resin :itself, .particularly if some of :the initial .solvent is apt to :remain without complete removal. .Even-if one starts with a resinywhich isalmost water-white in color, theproducts-pbtainedare almost invariably a dark red inzcolor or atigleast a red-amber, ,or somecolor which :includes :both an amber component and a reddish component. By and large, the:melting point {1S aptrtobe lower and the products may be :more sticky and more tacky than the original resin itself. Depending .on the resin selectedaandzon the amine selected .the ,condensation :product or reaction mass onasolvent-free basis may he hardresinous andcomparable to the resin itself.

The :products obtained, depending on the re.- actantsselected, may be water-insoluble, or water dispersible, or water-soluble, or close to being waters-soluble. Water solubility is enhanced,2. o f .course,-by makinga solution in the acidified .ve- :hicle such .as a dilute solution, for-.instancawa 15% solution of hydrochloric acid, acetic acid,.'hy- 'droxyacetic acid, etc. One also may .convertthe finished product into salts by simply :adding :a 'stoichiometricamount of any selected acid and removing any water present by refluxing with benzene .or-the like. Infact, the selection of the solvent employedmay depend in part whether .orcnotthe product at the completion of there- :actionris .to be converted into a salt form.

In .theLneXt. succeeding paragraph itis g-pointed outzthat frequently it .is convenient .to eliminate all solvent, using. a temperatureof not-over ;l-5,0 .C. and employing .vacuum,.if. required. This applies, oricourse, only toxthose circumstances where it isdesirableror necessaryto remove the solvent. Petroleum solvents, aromatic solvents, etc, canloe used. The selection of solvent, such as benzene, :xylenabr the like, depends primarily ,onpcost, li..-e., theuse of the most. economical solvent ,:and 'alsolon 'threeother factors, two of which have .been previously mentioned; (a) .is the solvent :to remainiin the reactionmass without removal? "(:b)1iscthe reaction mass to be subjected to further reaction in which the solvent, for instance, .an -alcohol,-. either low boiling or. high boiling-might case of .oxyalkylation? and this, (0) is an efiior't to be reaction mass by the usual ifany, or a water-wash to remove any unreacted .lowzmolalsoluble amine, if employed and. present zafterzreaction? Such procedures are well known and, :needless tosay, certain solvents are'more suitable than others. Everything else being equal,

I have found xylene the mostsatisfactorysolvent. I have 'found -no particular advantage inlusing a -'low temperature in the -early stage of "the reaction because, and for reasons explained, this is not necessary although it does apply insome other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, to but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, I am not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refiuxing should be long enough toinsure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out I prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if-there is any difiiculty with formaldehyde loss control, one can use a more hand, if the products are dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difiiculties are involved. I have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to 10-24 hours, I then complete the reaction by raising the temperature up to 159 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. I then. permit the temperature to rise to somewhere about C., and generally slightly above 100 (3., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,358.

Needless to say, as far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances I have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases I have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible I have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surfaceactivity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In the hereto attached claims reference is made to the product as such, i. e., the anhydro base. Needless to say, the hydrated base, i. e., the material as it combines with water or the salt form, with a combination of suitable acids as noted, is essentially the same material but is merely another form and, thus, the claims are intended to cover all three forms, i. e., the anhydro base, the free base, and the salts.

In light of what has been said previously, little more need be said as to the actual procedure employedfor the preparation of the herein described Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 20.. It was obtained from a paratertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. .e.. the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, .or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with 700 grams of xylene. The mixture we; refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 210 grams of diethanolamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 180 grams were employed which were added in about 3 hours. The mixture was stirred vigorously and kept Within a temperature range of 30 to 45 ,C. for about 21 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of unreaoted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was no longer detectable the phase-separating trap was set so as to :eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about 150 C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During thisv time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was in color and had the consistency of a sticky fluid or a tacky resin. The overall reaction time was a little over 30 hours. In other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

Note that in Table II following-there. are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 .to 150 01., or thereabouts. Usually the mixtureyielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Strength of R Max, Resin t, Formalde- Solvent Used Rea-emu Distill Ex. No. Used gm Amme Used and Amount hyde 80111.. and Amt. o 5 emp.,

and Amt, 0. 2a 882 Diethanolalnine, 210 g Xylene, 700 g 22-26 32 147 5a Diethanolamine, g Xylene, 450 g 21-23 28 150 10a (1 Xylene, 600g..- 20-22 36 2a Xylene, 400 g 20-23 34 146 5 Xylene, 450 g 21-23 24 141 10a Xylene, 600 g. 21-28 24 145 2a Xylene, 700 g. 20-26 24 152 5 Xylene, 450 g 24-30 28 151 10a Xylene, 600g. 22-25 27 147 13a Xylene, 45!) g2... 21-31 31 146 14a 0 22-23v 36 148 15a Xylene, 550 g. 20-24 27 152 I Xylene, 400 g 21-25 24, HO C2114 I 14b 5a 480 C2Hs 0021140 C211 H, 176 g do Xylene, 450 20-26 26 146 no (32H; 15b 9a 595 C2115!) C2310 C2114 NH, 176 g.. do Xylene, 550 g 21-27 30 147 HO C2H4 16b 2a 441 HO 02114 O C2H; O C2H4 N. 192g.--. .--..do Xylene, 400 g.. 20-22 30 148 HO elm" 17b 56 480 HO 021140 03114 O 01H;

N, 192 g..-- do :lo 20-25 28- 150 no 01H; 18b 142 591 HO C1340 C2H4Q (32H;

N. 192 s-.--. do

Xylene, 500 3-". 21-24. 32 149 no 01H 19 20 TABLE II-Continued Ex. No. g" Amine Used and Amount 223 gg igf 1 ;131:1 3? iliigg 3555 and Amt 19b 22a 498 HO CIHAO CIHO 01H;

7 N, m .do Xylene, 450 g.--. 22-25 32 153 N, 206 g 30%, 100 g... Xylene, 500 g.-. 21-23 36 151 HO Crib N, 206 gl.--...- do -.do 25-30 34 148 HO 01H;

22b 2a 441 CHKO 01114):

N, 206 g. do. Xylene, 400 g. 22-23 31 146 HO 01H: 23!; 260 595 Decylethanclamine, 201 g 37%, 81 g. Xylene, 500 g... 22-27 24 14!! 24b 27a 391 Decylethanolamine, 100 g 30%, 50 g. Xylene, 300 g... 21-25 26 14'! PART may be used admixed with some other chemical Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may b used alone or in admixture with other suitable wellknown classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicin the present or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 2'7, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also process, the treating demulsifier. A mixture which illustrates such combination is the following:

The product of Example 112, 20%

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulionic acid, 12%;

A high-boiling aromatic 15%;

Isopropyl alcohol, 5%.

The above proportions The compounds herein described and particularly those adapted for breaking petroleum emulsions although having other uses as noted in my co-pendingapplication, Serial No. 288,743, filed May 19, 1952, are derived from resins in which the bridge between phenolic nuclei is a methylene group or a substituted methylene group.

Comparable amine-modified compounds serving all these various purposes are obtainable from another class of resins, i. e., those in which the phenolic nuclei are separated by a radical having at least a B-carbon atom chain and are obtained, not by the use of a single aldehyde but by the use of formaldehyde, in combination with a carbonyl compound selected from the class of aldehydes and ketones in which there is an alpha hydrogen atom available as in the case of acetaldehyde or acetone. Such resins almost invariably involve. the use of a basic catalyst. Such bridge radicals between phenolic nuclei have either hydroxyl radicals, or carbonyl radicals, or both, and are petroleum solvent,

invariably oxyalkylation-susceptible and may:

also enter into more complicated reactants with basic secondary amines. The bridge radical in the initial resin has distinct hydrophile character. Such resins or compounds which can be readily converted into such resins are described in the following patents. Such analogous compounds are not included as part of the instant invention.

U. S. Patents Nos. 2,191,802, dated February 2'7, 1940, to Novotny et al.; 2,448,664, dated September '7, 1948, to File et al.; 2,538,883, dated January 23, 1951, to Schrimpe; January 23, 1951, to Schrimpe; March 20, 1951, to Schrimpe; 2,570,389, dated October 9, 1951, to Schrimpe.

are all weight percents.

2,538,884, dated 2,545,559, dated Having thus described :my' invention, what I claim as new and desire to secure by Letters Patent is:

1. A process for breakin petroleum emulsions of he water-in-oil type characterized by sub- J'ecting the emulsion to the action of a demulsifier including theproducts obtained in the process of condensing (a) an oxyalk-ylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight to at least ,3 and not over 6 per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived .by reaction between ,a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine havconducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oXyalkylation-susceptible.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the productsobtained in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average moleular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of conducted so as of the resultant ing the emulsion toxthe action of a demulsifier. in-

cluding the products obtained in the process of condensing (a) an oxyalkylation-susceptible, fnsible, non-oxygenated organic solvent-soluble,

stantial absence of trifunctional phenols said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated ing not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) has contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approxima-ely l, 2 and 2,

respectively; with the further proviso that said procedure involve the use of asolvent; and-with reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed'in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine hav ing not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants has contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants has contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated, organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde with the further proviso that said resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being diin which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having ,not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants has contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

7. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being I conducted at a temperature above the boiling bridge connecting the amino nitrogen atom with 32 carbon atoms in any group a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

8. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolformaldehyde resin having an average molecular weight corresponding to at least 3 and not over phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R, is an aliphatic hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the para position; (b) a basic hydroxylatecl secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants has contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oXyalkylation-susceptible.

9. The process of claim 1 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid; in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

10. The process of claim 2 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anyhdro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said are sufiicient to produce 2e xylene solution is shaken volumes of water.

11. The process of claim 3 with the proviso that I the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 4 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 5 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of Water.

14. The process of claim 6 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

15. The process of claim 7 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

16. The process of claim 8 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

vigorously with l to 3 References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,031,557 Bruson Feb. 18, 1936 2,457,634 Bond et al Dec. 28, 1948 2,499,365 De Groote et al Mar. 7, 1950 2,499,368 De Groote et al Mar. 7, 1950 2,570,377 Revukas Oct. 9, 1951 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 